Olfactory dioxolane derivatives and compositions containing same

ABSTRACT

DIOXOLANES WHEREIN THE DIOXLANE RING IS FUSED TO A SATURATED OR UNSATURATED 12-MEMBERED HYDROCARBON RING, AND CONSTIUTING A NOVEL SERIES OF OLFACTORY AGENTS, USEFUL IN PERFUMES, COSMETICS, DETERGENTS, SOAPS, ETC.

Patented Apr. 2, 1974 (b) Saturated trans 1,3 dioxolanes of the general 3,801,600 formula OLFACTORY DIOXOLANE DERIVATIVES AND 1 COMPOSITIONS CONTAINING SAME R Peter Naegeli, Unter-Ehrendingen, Switzerland, assignor +3,

to Givaudan Corporation, Clifton, NJ. 5 O No Drawing. Filed Dec. 30, 1970, Ser. No. 102,987 Claims priority, applicatziglzllgsvilzerland, Jan. 9, 1970,

Int. Cl. C07d 13/00 US. Cl. 260-3405 9 Claims 10 in;

(c) trans-trans-diene-cis-dioxolanes of the general for- ABSTRACT OF THE DISCLOSURE mula Dioxolanes wherein the dioxolane ring is fused to a saturated or unsaturated IZ-membered hydrocarbon ring, o R and constituting a novel series of olfactory agents, use- I ful in perfumes, cosmetics, detergents, soaps, etc. V

FIELD OF THE INVENTION Novel compounds having mushroom-like, earthy to w Woody woody-ambef'llke Odors- (d) Trans-trans-diene-trans-dioxolanes of the general DESCRIPTION OF THE PRIOR ART formula There is described in the Bull. Chem Soc. Jap., 36, p. 1390 (1963) a compound having the following formula: 0 R:

o C x O CH;

ID I (e) Cis-trans-diene-trans-dioxolanes of the general formula This compound is so devoid of odor qualities as to be of 0 R no practical interest in perfumery.

SUMMARY OF THE INVENTION x The present invention is concerned with new olfactory compounds of the general formula 40 CHz-A-CHg-CHz-A-CH; CHa-CH-CH H3 IE In the above Formulae LA-IE, R and R have the significance given earlier. I DESCRIPTION OF THE PREFERRED EMBODIMENTS wherein A signifies a The new compounds of General Formula I can be group, R and R independently of each other signify 5 manufactured in accordance with the invention by hydrogen or alkyl containing 1-3 C (such as methyl, Sub-tin a 1 col f th eneral f 1 ethyl, propyl, isopropyl) and R together with R signifies (a) J g g y e g mm a trior tetramethylene, and where the two A symbols CHa-A-CH,CH,-A-CH, represent CH=CH groups, one of these ethylene groups should display trans configuration and the other OH OH II should display cis or trans configuration and where, moreover, in the case of cis-trans configuration of the two wherein ethylene bonds the two oxygen atoms of the dloxolane A is as above and where, in case the two A symbols reprering should be translocated. Sent CH CH groups, one of these ethylene groups The Sub-groups (lolnpmhendad by the above defimtlon should display trans configuration and the other should X i can be represented by the following display cis or trans configuration and where, morem ae over, in case of cis-trans confi uration of the two (a) Saturated c1s-1,3-d1oxolanes of the general formula ethylene bonds, the two hydroxgy groups Should be E trans-located, o-i-n, to acid-catalyzed cyclization with a compound of the gen- 0 eral formula IA R R: 111

to catalytic hydrogenation for the purpose of producing a saturated compound of General Formula I (i.e. compounds of General Formulae IA and IB The wavy bonds leading to the oxygen atoms are meant to express that the Formulae I, II and IV comprehend both cisand trans-dioxolanes and cisand trans-glycols. The saturated compounds of General Formulae IA and IB can accordingly be obtained from saturated glycols of Formulae IIA and IIB respectively IIA IIB (cis-glycol) (trans-glycol) in accordance with process variant (a) or by catalytic hydrogenation of diene-dioxolanes of General Formula IV in accordance with process variant (b). Thus, the Compounds IA can, for example, be obtained by hydrogenation of dienes of General Formula 10 or of those of the general formula wherein R and R signify the same as above, and the Compounds'IB can, for example, be produced by hydrogenation of the dienes ID or IE.

The unsaturated Compounds '10, ID and IE can be manufactured from the corresponding unsaturated glycols IIC, IID and HE respectively H 0H OH OH OH IIC IID IIE (trans-trans-diene- (trans-trans-diene- (cls-trans-dienecis-glyeol) trans-glycol) trans-glycol) in accordance with process variant (a).

The acid-catalyzed cyclization according to process variant (a) can be undertaken according to the usual methods of ketalization or acetalization of ketones or aldehydes with 1,2-glycols. As acidic catalysts there can, for example, be used mineral acids, organic sulphonic acids (such as p-toluenesulphonic acid) or copper (II) sulphate. The reaction of the glycol H with the aldehyde or ketone III is expediently effected using an excess of carbonyl Compound III at temperatures between about 0 and 100 C., preferably at about room temperature. The ,reaction can be carried out with or without addition of solvents (such as aromatic or halogenated aliphatic hydrocarbons) as well as with or without addition or waterbinding agents (such as sodium sulphate, magnesium sulphate, Alox, silica gel, etc.). The starting glycols II are known compounds.

The hydrogenation in the sense of process variant (b) can likewise be undertaken according to methods which are known per se. As hydrogenation catalysts there can, for example, be mentioned palladium, platinum and Raney-nickel.

The compounds of General Formula I in accordance with the invention are distinguished by interesting odor properties, on the basis of which they can be used for perfumery purposes such as manufacture of odorant compositions (e.g. perfumes) or for perfuming products of all kinds (e.g. cosmetic products such as soaps, creams and further toilet articles, or household detergents such as washing powders). The content of the compounds of this invention in odorant compositions or in the perfumed products can vary within wide limits, for example between 0.1 to 15 wt. percent, the preferred range being from about 0.5% to 10%. In soaps, the weight percent is from 1 to 2%, in lotions and bath salts the corresponding amounts are 2 to 3% and 0.3 to 5% respectively of such odorant compositions.

The fragrance notes of the compounds of General Formula I can be characterized as mushroom-like, earthy to purely woody or woody-amber-like.

Cis-dodecahydro-2-methyl-cyclododeca[d] 1,3-dioxol (Formula 'IA: R =H, R =CH and trans-3a,4,5,8,9,12, 13,13a-octahydro 2,2 dimethyl-6-cis,10-trans-cyclododeca[d]-1,3-dioxol (Formula IE: R =CH R =CH are distinguished by particular odor qualities.

EXAMPLE 1 8.8 g. of cis-3a,4,5,8,9,12,13,13a-octahydro-2-methyl-6- cis, IO-trans-cyclododeca[d]-l,3-dioxol dissolved in ml. of pure ethanol were stirred in a hydrogen atomsphere in the presence of 50-0 mg. of 5 percent palladium-charcoal or 5 percent palladium on calcium carbonate until the uptake of hydrogen was completed. After filtration of the solution and evaporation of the solvent, there remained an oil which was distilled at 70 C./ 0.001 mm./'Hg. The colorless distillate (98% yield) is pure cis-dodecahydro- 2. methyl-cyclododeca[d] 1,3 dioxol (Formula IA: R =H, R =CH Odor: woody, green, fruity.

IR 1170, 1140, 1100 cmr NMR q. (1H) at 6:500 and 5.30 p.p.m.; m. (2H) at 8:3.96 ppm.

The dioxolane used as the starting material was obtained from the corresponding diol as follows:

30 g. of 5-cis, 9-trans-cyclododecadiene-1,2-cis-diol, 600 g. of paraldehyde, 1.5 g. of paratoluenesulphonic acid and 6 g. of anhydrous magnesium sulphate were intensively stirred at room temperature for two days. The reaction mixture was then poured onto cold dilute bicarbonate solution and exhaustively extracted with hexane. After washing neutral and drying the hexane phases, the solution was concentrated and filtered on the 15-fold amount of aluminium oxide. The colorless eluate (25 g.) was distilled at 100 C./0.001 mm./Hg and represents pure cis-3a,4,5,8,9,12,13,13a octahydro 2 methyl-6-cis, 10-trans-cyclododeca[d]-1,3-dioxol.

EXAMPLE 2 5 g. of trans-cyclododecane-1,2-diol, 300 mg. of paratoluenesulphonic acid and 50 ml. of pure acetone were stirred overnight at room temperature. The reaction solution was then poured onto cold dilute bicarbonate solution and extracted with hexane. After washing with water and drying with anhydrous sodium sulphate, the hexane phase was evaporated and the oily crude product filtered as a hexane solution on the 10-fold amount by weight of neutral aluminium oxide (Woelm, act. II). The eluate was evaporated and distilled at 65 C./0.001 mm. Hg. The

4.5 g. of colorless distillate are pure trans-dodecahydro- 2,2-dimethylcyclo ddeca[d] 1,3 dioxol (Formula IB: R =CH R =CH Odor: Woody.

IR 1385, 1375, 1245, 1100, 1070, 1045 cm.- NMR m. (2H) at 6=3.754.00 p.p.m.; s. (each 3H) at 6=l.33-l.37 p.p.m.

EXAMPLE 3 '6 g. of S-trans, 9-trans-cyclododecadiene-1,2-cis-diol, 200 mg. of para-toluenesulphonic acid, 1 g. of anhydrous magnesium sulphate and 150 ml. of paraldehyde were intensively stirred at room temperature for 3 days. The reaction mixture was then poured onto cold dilute bicarbonate solution and this extracted three times with hexane. The hexane phase were intensively washed with water. After drying and evaporation of the solvent, the oily crude product was filtered, in the form of a hexane solution, directly on the 15-fold amount by weight of neutral aluminium oxide (Woelm, act. II). The colorless eluate (4.5 g.) was directly distilled at 80 C./0.001 mm. Hg and represents pure cis 3a,4,5,8,9,12,13a octahydro-Z-methyl-6-trans, 10 -'trans cyclododeca[d] 1,3 dioxol (Formula IC: R =H, R =CH Odor: Woody, amberlike.

IR 1140, 1130, 1085/ 1075/975 cmr NMR: m. (4H) at 6=4.955.4 p.p.m.; m. (2H) at 6=3.8-4.2 p.p.m.; d. (3H) at 6:1.37 and 1.30 (J.'=5 c.p.s.).

EXAMPLE 4 4 g. of S-trans, 9-trans-cyclododecadiene-1,2-trans-diol, 300 mg. of para-toluenesulphonic acid and 40 ml. of pure acetone were stirred overnight at room temperature. The reaction solution was then poured onto cold dilute bicarbonate solution and extracted with hexane. After washing with water and drying with anhydrous magnesium sulphate, the hexane phase was concentrated and filtered on 40 g. of neutral aluminium oxide (Woelm, act. H). The eluates were combined, evaporated and distilled at 65 C./ 0.001 mm. Hg. The 3 g. of colorless liquid represent pure trans 3a,4,5,8,9,12,l3,13a octahydro 2,2 dimethyl-6- trans, 10 -trans cyclododeca[d] 1,3 dioxol (Formula ID: R =CH R =CH Odor: Woody, amber-like, fatty.

I'R 1380, 1370, 1240, 1220, 1170, 1130, 1090, 1060, 1025, 1010, 970, 878 cmr NMR z m. (4H) at 6=5.20-5.40 p.p.m.; m. (2H) at 6=3.90-4.15 p.p.m.; s. (6H) at 6:1.40 p.p.m.

EXAMPLE 5 5 g. of S-cis, 9-trans-cyclodecadiene-1,2-trans-diol, 300 mg. of para-toluenesulphonic acid, 50 ml. of cyclopentanone and 20 ml. of chloroform were intensively stirred at room temperature for 24 hours. The reaction solution was poured onto ice-cold dilute bicarbonate solution and exhaustively extracted with hexane. After washing and drying of the hexane phase, the solvent was evaporated off and the oily crude product directly distilled at 90 C./0.001 mm. Hg. The liquid colorless distillate (5.8 g.) represents pure 6-cis, -trans-3a,4,5,8,9,12,13,13a-octahydrospiro(trans-cyclododeca[d]-l,3-dioxol 2,1 cyclopentane) (Formula IE:

R +R =CH CH CH -CH Odor: Weakly woody, green.

IR 1665, 1340, 1210, 1115, 1050, 980, 742, 723, 706 cmr NMR m. (4H) at 6=5.15.7 p.p.m.; m. (2H) at 6=3.7-4.0 p.p.m.

EXAMPLE 6 5 g. of S-cis, 9-trans-cyclododecadiene-1,2-trans-diol, 300 mg. of para-toluenesulphonic acid, 3 g. of paraformaldehyde, 50 ml. of benzene and 50 ml. of methylene chloride were intensively stirred at 60 C. (bath-temperature) for 3 days. The reaction mixture was thereupon poured onto cold, dilute bicarbonate solution and exhaustively extracted with hexane. After washing and drying the hexane phase, the solvent was evaporated. The crude. material (5.8 g.) was filtered as a hexane solution through the 10-fold amount by weight of neutral aluminum oxide (Woelm, act. II) and, after evaporation, the hexane eluate was distilled at 60 C./0.001 mm. Hg. The colorless liquid distillate represents pure trans 3a,4,5,'8,9,12,13,l3aoctahydro-6-cis, IO-trans-cyclododeca[d]-1,3-dioxol (Formula IE: R =H, R =H). Odor: Woody, earthy.

IR 1665, 1450, 1100, 980, 740, 706 cmr NMR m. (4H) at 6=5.1-5.7 p.p.m.; s. (2H) at 6:4.95 p.p.m.; m. (2H) at 6=3.654.05 p.p.m.

EXAMPLE 7 Trans 3a,4,5,8,9,12,13,1-3a-octahydro 2,2 dimethyl-6- cis, 10 trans-cyclododeca[d]-1,3dioxol (Formula IE: 1= a, 2= 3) 10 g. of S-cis, 9-trans-cyclododecadiene-1,2-trans-diol were stirred for 24 hours at room temperature in ml. of absolute acetone together with 300 mg. of p-toluenesulphonic acid as catalyst. The reaction mixture was poured onto ice-water, the resulting mixture was thoroughly extracted with ether, the combined ethereal extracts were washed with bicarbonate solution and then with water, then dried and finally, the solvent was evaporated. The crude material was dissolved in hexane and filtered through the 10-fold amount (by weight) of alumina. The eluate was concentrated and gave, on distillation, 10 g. of pure trans3a,4,5,8,9,12,13,13a-octahydro- 2,2-dimethyl-6-cis, 10-trans-cyclododeca[d]-1,3-dioxol.

EXAMPLE 8 Trans 3a,4,5,8,9,12,13,13a-octahydro 2 methyl-G-cis, 10 trans-cyclododeca[d] 1,3 dioxol (Formula IE: R =H, R =CH odor: woody, amber-like, fresh 5 g. of 5-cis, 9 trans-cyclododecadiene-1,2-trans-diol were stirred for 24 hours at room temperature together with 300 mg. of p-toluenesulfonic acid in 50 g. of paraldehyde. The mixture was poured onto ice-water and the resulting mixture thoroughly extracted with hexane; the combined hexane layers were washed with saturated sodium carbonate solution and then with water, the organic phase was dried and the solvent evaporated 0E. The crude product was dissolved in hexane and filtered through the l0-fold amount (by weight) of alumina. The eluate was concentrated and then distilled in high vacuum. There were obtained 4.8 g. of pure trans-3a,4,5,8,9,12,13,132).- octahydro-2-methyl-6-cis, 10-trans-cyclododeca[d] 1,3- dioxol.

In a manner analogous to the teachings of the fore going examples, as will be understood by those skilled in the art, the compounds of the foregoing examples, Nos. 9 to 14 inclusive were prepared.

Trans 3a,4,5,8,9,12, 13,13a octahydro-2,2-diethyl-6- cis, 10-trans-cyclododeca[d] 1,3 dioxol (Formula IE: R =C H R =C H Odor: weakly woody.

EXAMPLE 11 Trans dodecahydro 2 methyl-cyclododeca[d]-1,3-

dioxol (Formula IB': R '=H, R =CH Odor: earthy, woody, atchouli-like.

EXAMPLE '12 Trans 3a,4,5,8,9,12,13,13a octahydro 2 methyl- 6-trans, 10-trans-cyclododeca[d]-l,3-dioxol (Formula ID:

= H, R =CH Odor: cedarwood-like, amber-like.

7 EXAMPLE 13 Cis dodecahydro 2,2 dimethylcyclododeca[d] 1,3- dioxol (Formula IA: R= CH R= CH Odor: woody, sweetish.

EXAMPLE 14 Cis 3a,4,5,8,9,12,13,13a octahydro-2,2-dimethyl-6- trans, 10-trans-cyclododeca[d]-1,3-dioxol (Formula IC: R =CH R =CH Odor: wood'y, fruity.

Analytical data relative to the compounds prepared in accordance with Exemples 1 through 14 follows.

Compound of Example 1:

C calc.: 74.28%; H calc.: 11.58%. C found: 74.03%; H found: 11.50%.

Compound of Example 2:

C calc.: 74.95%; H calc.: 11.74%. C found: 74.96%; H found: 11.80%.

Compound of Example 3:

MS: M/e=222; m/e=207, 178, 161, 149, 139, '134,

Compound of Example 4:

C calc.: 76.22%; H calc.: 10.24%. C found: 76.35%; H found: 10.38%.

Compound of Example 5:

C calc.: 77.82%; H calc.: 99.99%. C found: 77.82%; H found: 9.92%.

Compound of Example 6:

C calc.: 74.98%; H calc.: 9.68%. C found: 74.62%; H found: 9.85%.

Compound of Example 7:

C calc.: 76.22%; H calc.: 10.24%.

C found: 76.56%; H found: 10.09%.

1100, 1070, 11060, 975, 875, 740, 720 cmf NM'R m. (4H) at 6=5.0-5.8 p.p.m.; m. (2H) at 6=3.74.1 p.p.m.; s. (6H) at 6:1.38 p.p.m.

Compound of Example 9:

B.P. 80 C./0.001 mm. Hg.

C calc.: 76.75%; H calc.: 10.47%.

C found: 76.67%; H found: 10.43%.

NMR m. (4H) at 6=5.85.9 p.p.m.; m. (2H) at 6:3.65-415 p.p.m.; s. (3-H) at 6:1.30 p.p.m.; t. (3H, J.'=7 c.p.s.) at 6:0.9 p.p.m.

Compound of Example 10:

B.P. 85 C./0.001 mm. Hg.

C calc.: 77.22%; H calc.: 10.67%.

C found: 77.30%; H found: 10.87%.

IR 1660, 1360, 1280, 1205, 1178, 1140, 1100, 1080, 1060, 1042, 9'95, 978, 935, 740, 722 cmr NMR m. (4H) at 6=5.0-5.9 p.p.m.; m. (2H) at 6=3.75-4.1 p.p.m.; q. (4H, J.=7 c.p.s.) at 6:1.62 p.p.m.; t. (6H, J.==7 c.p.s.) at 8:0.90 p.p.m.

8 Compound of Example 11:

M.P. 53-54" C. C calc.: 74.28%; H calc.: 11.58%. C found: 73.99%; H found: 11.58%. IR 1422, 11392, 1240, 1170, 1150,1105, 1010,

880, 875, 700 cm.- NMR q. (llH, J. =5 c.p.s. )at 6= 5.18 p.p.m; m. (2 H) at 6=3.754.15 p.p.m.; d. (3H, J. ==5 c.p.s.) at 5:1.35 p.p.m. Compound of Example 12:

B.P. 65 C./0.001 mm. Hg. C calc.: 75.63%; H calc.: 9.97%. C found: 75.61%; H found: 10.15%. IR 1678, 1420, 1395, 1190, 1150, 1125, 1100,

1025, 975, 882 cm.- NMR m. (4 H) at 6=4.95.6 p.p.m.; q. (1H, J.=5 c.p.s.) at 5:5.15 p.p.m.; m. (2H) at 6:3.75 4.30 p.p.m.; d. (3H, J=5 c.p.s.) at 6:137 p.p.m. Compound of Example 13:

B.P. 70 C./0.001 mm. Hg. C calc.: 74.95%; H calc.: 11.74%. C found: 74.77%; H found: 11.91%. IR 1375, 1365, 1242, 1220, 1070, 1048, 870

cm. NMR m. (2H) at 6:3.80-430 p.p.m.; s. (3H) at 6:1.40 p.p.m.; s. (3H) at 6:1.32 p.p.m. Compound of Example 14:

B.P. C./0.00l mm. Hg. MS: M/e=236; m/e=221, 179, 161, 153, 149, 140,

1055, 1038, 975, 865 cm. NMR m. (4H) at 6=4.9-5.7 p.p.m.; m. (2H) at 6:3.8-43 p.p.m.; s. (3H) at 6:1.45 p.p.m.; s. (3H) at 6:1.35 p.p.m.

EXAMPLE 15 Composition (fantasy note) Parts by weight Cis dodecahydro 2-rnethyl-cyclododeca[d]-1,3-

dioxol (Formula Ia: R -=H, R =CH 30 Vanillin l0 Coumarin 10 Piperonal 20 Isocinnamyl alcohol 20 Beta-ionone 50 Alpha-ionone 1,1,3,3,5-pentamethyl-4,6-dinitroindane 30 p-Tert-butyl-cyclohexyl acetate 70 Sandalwood oil, East-Indian 20 Vetivenyl acetate 40 Benzoic Siam resinoid 20 Eugenol 30 Pimento oil 40 Isobutyl salicylate 80 Iris resinoid 20 Mimosa absolue (10% in phthalic acid diethyl ester) 40 Hydroxycitronellal 70 Ylang Ylang oil absolue 20 Rose de mai synth. 50 Gamma-nndecalactone (1% in phthalic acid diethyl ester) 30 Benzyl acetate 50 Decyl aldehyde (1% in phthalic acid diethyl ester) 20 Orange oil Ital. 30 Bergamotte oil Reggio -2 70 EXAMPLE 16 The addition of trans 3a,4,5,8,9,12,13,13a-octahydro- 2,2-dimethyl 6 cis, IO-trans-cyclododeca[d]-1,3-dioxol 9 (Formula IE: R =CH R =CH in an amount of 1-2 wt. percent to the following odorant composition has exalting action, i.e. brings about an improvement and rounding off of the floral character thereof.

Parts by weight Citronellol laevo 50 Phenylethyl alcohol 50 Lavandulol 20 Lemon oil Spanish 20 Linalyl acetate 20 Hydroxycitronellal 70 a-Methyl-fl-(p-tert. butylphenyl)-propiona1dehyde 30 Benzyl propionate 80 Indole in phthalic acid diethyl ester) 10 Ylang Ylang oil Bourbon 20 p-Tert-butql-cyclohexyl acetate 40 Alpha-methylionone 50 Musk ketone 30 Musk ambrette 20 Piperonal 30 Coumarin 10 Civet nat. defatted (10% in phthalic acid diethyl ester) 20 Jasmin synthetic 40 Geranium oil Bourbon 10 Neroli oil synthetic 10 Undecylenaldehyde (10% in phthalic acid diethyl ester) 20 Jasmonyl Givaudan (isomeric mixture of nonane- 1,3-diol monoacetates) 30 Gamma-undecalactone (1% in phthalic acid diethyl ester) 20 What is claimed is:

1. A compound of the formula CHg-A-CHg-CHg-A-JEH: H;-CHCH-- H,

6 6 Rt Ra I wherein A signifies a --CH CH,-- or -CH=CH-- group, R and R independently of each other signify hydrogen or alkyl containing 1-3 C and R together with R signifies trior tetramethylene, and where, in case the two A symbols represents --CH=CH groups, one of these ethylene groups has trans configuration and the other has cis or trans configuration, and where, in case of cistrans configuration of the two ethylene bonds, the two oxygen atoms of the dioxolane ring are trans-located.

2. A cis-dioxolane in accordance with claim 1, having the formula 10 3. A trans-dioxolane in accordance with claim 1, having the formula 4. A trans-trans-diene-cis-dioxolane in accordance with claim 1, having the formula I o-i zi 5. A transtrans-diene-trans dioxolane in accordance with claim 1, having the formula 6. A cis-trans-diene-trans-dioxolane in accordance with claim 1, having the formula 7. A compound in accordance with claim 1, having the formula: cis dodecahydro-Z-methyl-cyclododeca[d]-1,3- dioxol.

*8. A compound in accordance with claim 1, having the formula: trans 3a,4,5,8,9,12,13,13a-octahydro-2,2-di methyl--cis, IO-trans-cyclododeca[d]-1,3-dioxol 9. A compound in accordance with claim 1, having the formula: trans-3a,4,5,8,9,12,13,13a-octahydro-2-methyl-6- cis, 10-trans-cyc1ododeca[d]-1,3-dioxol.

References Cited Takahasi: Chemical Abstracts, vol. (1964), col. 3998h-99a.

Takahasi: Chemical Abstracts, vol. 67 {1967), col. 53755q.

DONALD G. DAUS, Primary Examiner I. H. TURNIPSEED, Assistant Examiner U.S. Cl. X.R. 252--522 

